Olefin (co)polymerization where the olefins contain certain functional groups such as silyl may be carried out using certain transition metal compounds as catalysts. Olefins containing other functional groups such as ester or alkenyl may be similarly polymerized and/or the polymerization improved if the olefin contains a xe2x80x9cblocking groupxe2x80x9d such as a quaternary carbon atom.
Polyolefins are useful in many areas as, for example, molding resins for toys and automotive parts, resins for film in packaging, elastomers and other uses. Many times it is desirable to copolymerize an olefin containing one or more functional groups, which may serve to later help crosslink the polymer, change the surface or other physical properties of the polymer, etc. Many olefins may be polymerized by using various transition metal compounds as polymerization catalysts, such as Ziegler-Natta or metallocene-type catalysts. However many times these polymerizations either won""t proceed or proceed poorly in the presence of olefins containing functional groups.
Olefins may also be polymerized using catalysts containing late transition metals such as palladium or nickel, and sometimes functionalized olefins may be copolymerized. However, the range of useful functionalized olefins is limited, and often the efficiency of the polymerization is reduced in the presence of these olefins. Therefore more versatile and/or more efficient polymerizations of functionalized olefins are desired.
World Patent Applications 96/23010 and 97/02298 describe the polymerization of olefins, some of them containing functional groups, using certain transition metal containing compounds. The use of olefins containing blocking groups is not described in these applications.
This invention concerns a process for the polymerization of olefins, comprising, contacting a first olefin selected from the group consisting of cyclopentene, norbornene, and a compound of the formula R1CHxe2x95x90CHR1, a second olefin containing one or more of the functional groups selected from the group consisting of xe2x80x94SiR23, xe2x80x94CO2R3, a nonconjugated ketone, xe2x80x94SO2R7, alkenyl, xe2x80x94C(O)xe2x80x94Oxe2x80x94C(O)R4, xe2x80x94C6F5, xe2x80x94OR8, xe2x80x94CO2H, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94BR62, xe2x80x94SR9, xe2x80x94SH, ether, epoxy, and xe2x80x94CONR68R69, and a nickel or palladium coordination compound of 
Ar1Zp (VIII);
R31R32Nxe2x80x94CR33R34(CR35R36)mxe2x80x94NR31R32 (IX); 
R47R48R49Pxe2x80x83xe2x80x83(XXII);

and
R31Sxe2x80x94CR33R34(CR35R36)mxe2x80x94SR31 (XXIV);
wherein:
Ar1 is an aromatic moiety with n free valencies, or diphenylmethyl;
each Z is xe2x80x94NR52R53 or xe2x80x94CR54xe2x95x90NR55;
p is 1 or 2;
E is 2-thienyl or 2-furyl;
each R52 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
each R54 is independently hydrogen or hydrocarbyl; and
each R55 is independently a monovalent aromatic moiety;
m is 1, 2 or 3;
R53 is hydrogen or alkyl;
each R33, R34, R35, and R36 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R31 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
each R32 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar2 is an aryl moiety;
R38, R39, and R40 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R37 and R41 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose ES is about xe2x88x920.4 or less;
each R42 and R43 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
Ar3 is an aryl moiety;
R45 and R46 are each independently hydrogen or hydrocarbyl;
Ar4 is an aryl moiety;
Ar5 and Ar6 are each independently hydrocarbyl;
Ar7 and Ar8 are each independently an aryl moiety;
Ar9 and Ar10 are each independently an aryl moiety or xe2x80x94CO2R56, wherein R56 is alkyl containing 1 to 20 carbon atoms;
Ar11 is an aryl moiety;
R50 is hydrogen or hydrocarbyl;
R51 is hydrocarbyl or xe2x80x94C(O)xe2x80x94NR50xe2x80x94Ar11;
R44 is aryl;
R47 and R48 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
R49 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
R13 and R16 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R14 and R15 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R14 and R15 taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
R18 is hydrocarbyl or substituted hydrocarbyl, and R20 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R18 and R20 taken together form a ring;
R19 is hydrocarbyl or substituted hydrocarbyl, and R21 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R19 and R21 taken together form a ring;
each R17 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R17 taken together form a ring;
R27 and R30 are independently hydrocarbyl or substituted hydrocarbyl;
R28 and R29 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and
n is 2 or 3;
xe2x80x83which is an olefin polymerization catalyst, and wherein:
each R1 is independently hydrogen or alkyl;
each R2 is independently hydrocarbyl, substituted hydrocarbyl, halogen, acyloxy, amino, siloxy, or xe2x80x94OR12;
R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R4 is hydrocarbyl or substituted hydrocarbyl;
each R5 is independently hydrocarbyl or substituted hydrocarbyl;
R6 is hydrocarbyl or substituted hydrocarbyl;
R7 is hydrocarbyl or substituted hydrocarbyl;
R8 is hydrocarbyl or substituted hydrocarbyl;
R9 is hydrocarbyl or substituted hydrocarbyl; and
R68 and R69 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
xe2x80x83and provided that:
when said functional group is alkenyl, xe2x80x94OR8, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94SR9, xe2x80x94SH, ether, epoxy, or xe2x80x94CONR68R69 there is a blocking group between a carbon-carbon double bond of said olefin containing one or more of the functional groups and said functional groups; and
when said functional group is a nonconjugated ketone, alkenyl, xe2x80x94C(O)xe2x80x94Oxe2x80x94C(O)R4, xe2x80x94CO2H, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94SR9, or xe2x80x94SH, epoxy, said coordination compound is preferably a palladium compound.
Also disclosed herein is a compound of the formula H2Cxe2x95x90CHxe2x80x94Txe2x80x94NR71xe2x80x94C(O)CFR72(OCF2CFR72)aOCF2(CFR72)bSO2F, (XXVI), wherein:
T is alkylene or substituted alkylene;
R71 is hydrocarbyl or substituted hydrocarbyl;
each R72 is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2; and
b is 0 or an integer of 1 to 6.
Also disclosed herein is a copolymer comprising repeat units of the formula 
wherein:
T is alkylene or substituted alkylene;
R71 is hydrocarbyl or substituted hydrocarbyl;
each R72 is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2;
b is 0 or an integer of 1 to 6;
R73 is alkyl or hydrogen; and
R74 is hydroxyl, fluorine, chlorine, or OM, wherein M is a metal cation.
In the polymerization processes and catalyst compositions described herein certain groups may be present. By hydrocarbyl is meant a univalent radical containing only carbon and hydrogen. By saturated hydrocarbyl is meant a univalent radical which contains only carbon and hydrogen, and contains no carbon-carbon double bonds, triple bonds and aromatic groups. By substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more (types of) substitutents that does not interfere with the operation of the polymerization catalyst system. Suitable substituents include halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. Preferred substituents are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide. By (substituted) hydrocarbylene is meant a group analogous to hydrocarbyl, except the radical is divalent. By alkylene is meant a divalent radical in which the free bonds are to carbon atoms which are saturated. By substituted alkylene is meant substitution as described above for substituted hydrocarbyl. By benzyl is meant the C6H5CH2xe2x80x94 radical, and substituted benzyl is a radical in which one or more of the hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl). By an aryl moiety is meant a univalent group whose free valence is to a carbon atom of an aromatic ring. The aryl moiety may contain one or more aromatic ring and may be substituted by inert groups. By phenyl is meant the C6H5xe2x80x94 radical, and a phenyl moiety or substituted phenyl is a radical in which one or more of the hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl). Preferred substituents for substituted benzyl and phenyl include those listed above for substituted hydrocarbyl, plus hydrocarbyl. If not otherwise stated, hydrocarbyl, substituted hydrocarbyl and all other groups containing carbon atoms, such as alkyl, preferably contain 1 to 20 carbon atoms.
Where applicable, ES refers to the steric effect of a group. The steric effect of various groupings has been quantified by a parameter called ES, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p. 3120-3128 (1952), and M. S. Newman, Steric Effects in Organic Chemistry, John Wiley and Sons, New York, 1956, p. 598-603. For the purposes herein, the ES values are those described in these publications. If the value for ES for any particular group is not known, it can be determined by methods described in these publications. For the purposes herein, the value of hydrogen is defined to be the same as for methyl. It is preferred that the total ES value for the ortho (or other substituents closely adjacent to the xe2x80x94OH group) substitutents in the ring be about xe2x88x921.5 or less, more preferably about xe2x88x923.0 or less. Thus in a compound such as 2,4,6-tri-t-butylphenol only the ES values for the 2 and 6 substituted t-butyl groups would be applicable.
Noncoordinating ions are mentioned and useful herein. Such anions are well known to the artisan, see for instance W. Beck., et al., Chem. Rev., vol. 88, p.1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Relative coordinating abilities of such noncoordinating anions are described in these references, Beck at p. 1411, and Strauss at p. 932, Table III. Useful noncoordinating anions include SbF6xe2x88x92, BAF, PF6xe2x88x92, or BF4xe2x88x92, wherein BAF is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.
A neutral Lewis acid or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system. By a xe2x80x9cneutral Lewis acidxe2x80x9d is meant a compound which is a Lewis acid capable of abstracting Qxe2x88x92 or Sxe2x88x92 from (XXV) to form a weakly coordinating anion. The neutral Lewis acid is originally uncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF5, Ar3B (wherein Ar is aryl), and BF3. By a cationic Lewis acid is meant a cation with a positive charge such as Ag+, H+, and Na+.
In those instances in which (XXV) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid), does not contain an alkyl or hydride group already bonded to the metal (i.e., neither Q or S is alkyl or hydride), the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal, i.e., causes an alkyl group or hydride to become bonded to the metal atom, or a separate (from W) compound is added to add the alkyl or hydride group.
A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R93Al, R92AlCl, R9AlCl2, and xe2x80x9cR9AlOxe2x80x9d (alkylaluminoxanes), wherein R9 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO]n), (C2H5)2AlCl, C2H5AlCl2, and [(CH3)2CHCH2]3Al. Metal hydrides such as NaBH4 may be used to bond hydride groups to the metal M.
In the polymerization process herein the first olefin, which may be of the formula R1CHxe2x95x90CHR1 is copolymerized with a second olefin. In preferred first olefins, both of R1 are hydrogen (the olefin is ethylene), or one of R1 is hydrogen and the other is n-alkyl containing 1 to 20 carbon atoms. In the latter compound it is preferred that the n-alkyl group contains 1 carbon atom (the olefin is propylene). More than one first olefin and/or second olefin may be used, but at least one of each must be used.
The second olefin is a functional olefin that contains another group besides the carbon-carbon alkenyl double bond (the other functional group may also be a carbon-carbon alkenyl double bond). These two groups in the second olefin may (in some cases must) be separated by a blocking group. By a blocking group is meant a group that will not allow the carbon-carbon double bond and/or the functional group to isomerize so that these two groups may be directly conjugated to each other. By directly is meant there are no intervening groups between the two subject groups. The blocking group should not be able to readily form a xcfx80-benzyl group or a polymerizable vinyl ether group with the carbon-carbon double bond under the polymerization conditions, so p-phenylene or a simple aliphatic ether group such as xe2x80x94CH2CH2Oxe2x80x94 are not blocking groups. However, tetrafluoro-p-phenylene and an ether such as xe2x80x94CH2CH2OCF2CF2xe2x80x94 are blocking groups since they are so electron poor that they normally don""t readily form xcfx80-benzyl group or a polymerizable vinyl ether group, respectively. Useful blocking groups include a quaternary carbon atom (a carbon atom bound to 4 other atoms, none of which is a hydrogen atom, in other words the quaternary carbon atom does not have any multiple bonds to any other element), an ester group, an amide group, a sulfone group, tetrafluoro-p-phenylene, a silyl group, a borane group, a carbonate group, and ammonium cation. Preferred blocking groups are a quaternary carbon atom, especially a quaternary carbon atom bound to 4 other carbon atoms, an ester group, a sulfone group, and xe2x80x94(CF2)nxe2x80x94 wherein n is an integer of 2 to 20. Note that some blocking groups may also be the xe2x80x9cfunctionalxe2x80x9d groups of the second olefin. Whether a blocking group is required in a certain second olefin or not, it has been found that the yield of polymer when a blocking group is present is often greatly improved over using a functional olefin which does not contain a blocking group (if any polymer is obtained at all in the latter case). It is therefore preferred in all second olefins herein to have a blocking group present.
The polymers made herein are copolymers of the first and second olefins, although homopolymers of the second olefin may also be made if the first olefin is not present in the polymerization. Many of the copolymers made herein are unique since olefin copolymers with containing these functional groups have not been made. Such copolymers may include those with the functional groups such as xe2x80x94SiR23, a nonconjugated ketone, xe2x80x94SO2R7, alkenyl, xe2x80x94C(O)xe2x80x94Oxe2x80x94C(O)R4, xe2x80x94C6F5, xe2x80x94OR8, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94BR62, xe2x80x94SR9, xe2x80x94SH, ether, epoxy, and xe2x80x94CONR68R69, particularly if a blocking group is also present in the second olefin. In addition these polymers may have branching patterns that are xe2x80x9cabnormalxe2x80x9d in the sense that branches may be present that do not correspond to the branch expected if the olefin is simply incorporated into the polymer through the existing olefinic bond. For a discussion of such branching, see World Patent Applications 96/23010 and 97/02298. In addition to the abnormal number of carbon atoms in such branches and/or the abnormal number of branches, in some instances the functional groups of the second monomer may be present at the end of branches of the xe2x80x9cwrongxe2x80x9d length. Such polymers may also be novel.
Preferred functional groups in the second olefin are xe2x80x94SiR23 wherein all of R2 are chlorine or xe2x80x94OR70 wherein R70 is n-alkyl containing 1 to 6 carbon atoms, epoxide or alkenyl.
In olefins in which the xe2x80x94SiR23 group is present a preferred formula is H2Cxe2x95x90CH(CH2)qSiR23 wherein q is 0 or an integer of 1 to 20, more preferably an integer of 1 to 8. It is preferred that at least one of R2 is chloro or xe2x80x94OR57, wherein R57 is alkyl containing 1 to 20 carbon atoms, more preferably methyl or ethyl, and the remainder of R2 are alkyl containing 1 to 6 carbon atoms or phenyl, more preferably methyl. In one preferred form, all of R2 are chloro or xe2x80x94OR57.
Preferred olefins in which xe2x80x94CO2R3 are present have the formula 
wherein q is 0 or an integer of 1 to 20, R58 and R59 are hydrocarbyl or substituted hydrocarbyl, preferably alkyl containing 1 to 20 carbon atoms, and R60 is a covalent bond or alkylene containing 1 to 20 carbon atoms. In more preferred olefins of this type, q is 1 and/or R58 and/or R59 are methyl, and R60 is a covalent bond or xe2x80x94(CH2)sxe2x80x94 wherein s is an integer of 1 to 6, and/or R3 is alkyl or hydrogen.
Preferred olefins which have an amide group present have the formula 
wherein R58, R59, R60, R66, R67 and q are as defined above. In all amides it is preferred that R66 and R67 are hydrocarbyl or substituted hydrocarbyl. Preferred groups for R58, R59, R60 and q are as described above.
When the functional group in the second olefin is alkenyl, it is preferred that it has the formula 
wherein q is 0 or an integer of 1 to 20, R58 and R59 are hydrocarbyl or substituted hydrocarbyl, preferably alkyl containing 1 to 20 carbon atoms, R60 is a covalent bond or alkylene containing 1 to 20 carbon atoms, and R61 is hydrogen or alkyl containing 1 to 20 carbon atoms. In more preferred olefins of this type, q is 1 and/or R58 and/or R59 are methyl, and/or R60 is a covalent bond or xe2x80x94(CH2)sxe2x80x94 wherein s is an integer of 1 to 6, and/or R61 is hydrogen or methyl.
When the second olefin contains ether a preferred formula for the ether bearing moiety is 
wherein R12 is alkyl containing 1 to 20 carbon atoms, more preferably is methyl, or 
wherein R58, R59, R60, R66, R67 and q are as defined above, and R68 is hydrocarbyl or substituted hydrocarbyl, more preferably alkyl containing 1 to 20 carbon atoms. Preferred groups for R58, R59, R60 and q are as described above.
When the functional group is an epoxide, a preferred compound is 
wherein each of R10 is hydrogen, hydrocarbyl or substituted hydrocarbyl, R11 is hydrocarbyl or substituted hydrocarbyl, and q is 0 or an integer of 1 to 20, or a compound of the formula 
wherein q, R58, R59, R60 and R10 are as defined above. In preferred epoxides q, R58, R59, R60 are as defined above for preferred compounds, and/or R11 is preferably alkyl, more preferably methyl, and/or R11 is alkyl, more preferably methyl. Note that a quaternary carbon atom in the epoxide ring itself may act as a blocking group.
When the functional group in the second olefin is a nonconjugated ketone, a preferred olefin is H2Cxe2x95x90CHR64C(O)R65, wherein R64 is alkylene containing 1 to 20 carbon atoms and R65 is alkyl containing 1 to 20 carbon atoms. In more preferred olefins R64 is xe2x80x94(CH2)sxe2x80x94 wherein s is an integer of 1 to 6, and/or R65 is methyl.
Of the compounds (or their complexes) (IV) through (XXIV) used in the polymerization processes, (IV) is preferred. In all cases herein where (IV) appears, including as a ligand, it is preferred that R13 and R16 are each independently hydrocarbyl provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and R14 and R15 are each independently hydrogen, hydrocarbyl, or R14 and R15 taken together are hydrocarbylene to form a ring. Some useful combinations and/or individual groupings for R13, R14, R15 and R16 are shown in Table 1.
To indicate substitution on a phenyl ring, the nomenclature is abbreviated, the number of ring positions indicating how many of the substituents are on the ring. For instance, 4-Br-2,6-MePh indicates 4-bromo-2,6-dimethylphenyl.
For (IV) through (XXIV) preferred formulas and compounds (as ligands for polymerization catalysts) are found in World Patent Applications 96/23010 and 97/02298, both of which are hereby included by reference, and preferred grouping and compounds in these applications are also preferred herein. However the compound numbers and group (i.e., Rx) numbers in these Applications may vary from those herein, but they are readily convertible.
There are many different ways of preparing active polymerization catalysts of Ni or Pd coordination compounds of compounds (IV) through (XXIV), many of which are described in World Patent Applications 96/23010 and 97/02298, and those so described are applicable herein. xe2x80x9cPurexe2x80x9d compounds which themselves may be active polymerization catalysts may be used, or the active polymerization catalyst may be prepared in situ by a variety of methods.
For instance, olefins may be polymerized by contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C. a first compound W, which 20 is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or Sxe2x88x92 to form WQxe2x88x92 or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the formula 
and one or more olefins wherein:
M is Ni or Pd;
R13 and R16 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R14 and R15 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R14 and R15 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
Q is alkyl, hydride, alkoxide, chloride, iodide, or bromide; and
S is alkyl, hydride, alkoxide, chloride, iodide, or bromide.
In this instance it is preferred that W is an alkyl aluminum compound. Other methods for preparing active polymerization catalyst will be found in these patent application and in the Examples herein.
Which polymerization catalysts or types of catalysts will polymerize the first olefin types herein will also be found in World Patent Applications 96/23010 and 97/02298. It is believed that any catalyst that will polymerize xcex1-olefins of the formula H2Cxe2x95x90CHR66 wherein R66 is n-alkyl will also copolymerize any of the second olefins herein. First monomers useful herein include ethylene, propylene, other xcex1-olefins of the formula R67CHxe2x95x90CH2, wherein R67 is n-alkyl containing 2 to about 20 carbon atoms, cyclopentene, norbornene, and 2-butene. Preferred monomers are ethylene, propylene and cyclopentene.
Likewise, conditions for such polymerizations will also be found in these patent applications. Briefly, the temperature at which the polymerization is carried out is about xe2x88x92100xc2x0 C. to about +200xc2x0 C., preferably about xe2x88x9220xc2x0 C. to about +80xc2x0 C. The polymerization pressure which is used with a gaseous olefin is not critical, atmospheric pressure to about 275 MPa, or more, being a suitable range. With a liquid monomer the monomer may be used neat or diluted with another liquid (solvent) for the monomer. The ratio of W:(XXV), when W is present, is preferably about 1 or more, more preferably about 10 or more when only W (no other Lewis acid catalyst) is present. These polymerizations may be batch, semi-batch or continuous processes, and may be carried out in liquid medium or the gas phase (assuming the monomers have the requisite volatility). These details will also be found in World Patent Applications 96/23010 and 97/02298.
In (XXVI) and (XXVIII), where applicable, it is preferred that T is xe2x80x94(CH2)nxe2x80x94 wherein n is an integer of 1 to 10, more preferably n is 1, and/or R71 is alkyl, more preferably methyl, and/or each R72 is fluorine or trifluoromethyl, more preferably fluorine, and/or a is 0, and/or b is 1, and/or R74 is fluorine, hydroxyl or OM, wherein M is an alkali metal cation. In (XXVII) it is preferred that R73 is hydrogen or n-alkyl, more preferably hydrogen or methyl and especially preferably hydrogen.
(XXVI) may be made generally as described herein in Example 40 by the reaction of the appropriate alkenyl secondary amine with and acyl halide of the appropriate fluorinated sulfonyl fluoride. Such fluorinated sulfonyl fluorides can be made by methods known in the art, see for instance Siegemund, et al., in Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A11, VCH Verlagsgesellschaft mbH, Weinheim (1988), p. 374 and M. Yamabe, et al., in Organofluorine Chemistry: Principles and Commercial Application, R. E. Banks, et al., Ed., Plenum Press, New York (1994), p. 403-411.
Formation of polymers made from repeat units comprising (XXVII) and (XXVIII) can be made by methods described herein, see for instance Example 41. Once the polymer in which (XXVIII) is present and in which R74 is fluorine is made, the other derivatives with different groups for R74 can be made. For example, the fluorine may be converted to chlorine by reaction with a silicon chloride. The sulfonyl fluoride may be hydrolyzed by reaction with water to the sulfonic acid. If a base is present during the hydrolysis, such as an alkali metal hydroxide, the metal salt will be formed. It will be realized by the artisan that for other than monovalent metal is cations, an appropriate ratio of metal to sulfonate groups must be present to balance the ionic charges, and the group xe2x80x9cOMxe2x80x9d is meant to include such balancing. The sulfonic acid and sulfonate salts may be readily interconverted by reaction with a strong acid or strong base, as appropriate.
The polymers made herein are useful as molding resins, elastomers, in adhesives and for films. Because of the presence of functional groups they may be readily crosslinkable, have useful surface properties, or be especially compatible with other polymers.
In the Examples, the following abbreviations are used:
DSCxe2x80x94Differential Scanning Calorimetry
FTIRxe2x80x94Fourier transform infrared spectroscopy
GPCxe2x80x94Gel Permeation Chromatography
MAOxe2x80x94methylaluminoxane
MMAOxe2x80x94modified (contains sec-butyl groups) MAO
Mnxe2x80x94number average molecular weight
Mwxe2x80x94weight average molecular weight
PExe2x80x94polyethylene
PMAOxe2x80x94see MAO
RTxe2x80x94room temperature
TCBxe2x80x941,2,4-triclhorobenzene
TCExe2x80x941,1,2,2-tetrachloroethane
Tgxe2x80x94glass transition temperature (measured by DSC at 10xc2x0 C./min, the midpoint of the transition taken as the Tg)
THFxe2x80x94tetrahydrofuran
In the Examples transition metal complexes of (IV) are indicated by the use of the abbreviation xe2x80x9cDABxe2x80x9d. Immediately before the DAB are the groups represented by R13 and R16, while immediately after DAB are the groups represented by R14 and R15. The other groups coordinated to the metal and/or free anions present in the compound are also indicated.